Azo dye from an ortho-oxydiazolylaniline diazo component

ABSTRACT

Azo dyes derived from ortho-oxdiazolylaniline diazo components and from coupling components containing a hydroxy group or an enolizable keto group in ortho- or para-position to the azo bridge. The dyes are yellow to red and are useful as disperse dyes and particularly as pigments. The pigments give fast colorations in printing inks, resins and surface coatings.

United States Patent Dimroth et a1. 1 1 Dec. 2, 1975 [541 AZO DYE FROM AN 2,901,473 8/1959 Steinemzlnn 260/157 ORTIKLOXYDIAZOLYLANILINE DIAZO 3,398,134 8/1968 Bull ct a1 260/157 COMPONENT 3,473,928 10/1969 5115 260/157 [75] Inventors: Peter Dimroth; Ernst Schaifner, FOREIGN PATENTS OR APPLICATIONS both f Ludwigshafen, Germany 352,427 4/1961 Switzerland 260/157 731 Assignee: Badische-Anilin & Soda-Fabrik OTHER PUBLICATIONS Aktiengesellschaft, Ludwigshafen Nippon, Derwent Japanese Patents Report, Vol. 5, (Rhine), Germany N0. 3, pp. 2:7-218 (2-11-66). Nippon, Derwent Japanese Patents Report," Vol. 5, [22] F1led. July 5, 1973 No. 37 pp 2:8.(10 17 66) [21] Appl. No.: 376,565

, Primary Examiner-Henry R. Jiles Assistant ExaminerR0bert W. Ramsuer [30] Foreign Apphcamn Priority Dam Attorney, Agent, or Firm1ohnston, Keil, Thompson July 10. 1972 Germany 2233871 & Shumeff [52] U.S. CI 260/157; 106/23; 117/161 K;

260/25; 260/37 NP; 260/38; 260/42.21;' [57] ABSTRACT 2 0M24 Azo dyes der ved from ortho-oxd1azo1ylan1l1ne d1azo [51 1111.01. c091; 29/20 Components and from coupling Components contain- [58] Field of Search 260/152, 157, 156, 155 ing a y y group or an elwlizable kew group in thoor para-position to the azo bridge. The dyes are 5 References Cited yellow to red and are useful as disperse dyes and par- UNITED STATES PATENTS ticularly as pigments. The pigments give fast colorations in printing inks, resins and surface coatings. 2,195,011 3/1940 Pet1tcolas et a1. 260/157 7 2,313,738 3/1943 Dickey et a1 260/156 5 Claims, N0 Drawings 2/1959 Kracker et a1. 260/157 AZO DYE FROM AN 1 ORTHO-OXYDIAZOLYLANILINE DIAZO COMPONENT The invention relates to dyes of the formula (I):

in which K is the radical of a coupling component which contains a hydroxy groupor an enolizable ketogroup in the ortho-position or the para-position to the azo bridge; 1 a 1 R is an unsubstituted or substituted aliphatic, cycloaliphatic, araliphytic or aromatic radical, and the radical A may bear one or more substituents.

Examples of substituents for the radical -A are: bromo, methyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, phenyl, cyano and particularly chloro and mtro.

Examples of radicals R are alkyl of one to eight carbon atoms which may bear hydroxy, alkoxy of one to four carbon atoms, cyano, acyloxy, carbamoyl or N- substituted carbamoyl as a substituent, cyclohexyl, benzyl, phenylethyl, styryl, phenyl, phenyl bearing halogen, alkyl, alkoxygcyano, nitro, sulfamoyl, N-substituted sulfamoyl, arylsulfonyl or acylamino as a substituent, naphthyl or anthraquinonyl.

Examples of individual radicals R in addition to those already specified are: methyl, butyl, B-ethylhexyl, cyanomethyl, B-hydroxyethyl, B-ethoxyethyl, B-butoxyethyl, acetoxymethyl, carbamoylmethyl, N,N-dimethylcarbamoylmethyl, chlorophenyl, dichlorophenyl, methylphenyl, methoxyphenyl, methoxychlorophenyl, methoxydichlorophenyl, methylchlo'rophenyl, cyanophenyl, nitrophenyl, nitrochlorophenyl, nitrornethoxyphenyl, nitr omethylphenyl, sulfamoylphenyl, N-

phenylsulfamoylphenyl, N-dichlorophenylsulfamoylphenyl, phenylsulfonylphenyl, acetylaminopheny], benzoylaminophenyl, dichlorobenzoylaminophenyl or naphthoylaminophenyl.

Compounds of the phenol, naphthol, acetoacetarylide, pyrazolone, quinolone, pyridone, pyrimidone or isoquinolone series are suitable as coupling components.

Examples of individual coupling components are phenol, o-cresol, m-cresol, p-cresol, a-naphthol, B-

:naphthol, 2-naphthol-3-carboxylic esters, 2-naphtholand to convert this into a dye amide by a conventional method by reaction with an appropriate amine.

Dyes suitable as pigments are particularly compounds of the formula (I) in which R is an aromatic radical and K is the radical of a coupling component of the B-naphthol, acetoacetarylide, pyrimidine, dihydroxyquinoline or dihydroxypyridine series. These dyes are distinguished by great insolubility in solvents and as pigments they almost always have good fastness to overlacquering, migration and overspraying as well as very good fastness to light. They may therefore be used in printing inks, surface coatings or plastics such as PVC. I

Pigments of formula (I) are not always in the optimal physical form for the special purpose of application. They may be converted into the most suitable form however by conventional methods such as grinding with salt, heating in water or solvents.

Other dyes of the formula (I) and particularly those in which R is an aliphatic radical and the coupling component originates from the cresol, N-alkylpyrimidine, N-alkylpyridine or N-alkylquinoline series are good disperse dyes which are preferably suitable for dyeing polyester fibers and give'dyeings having good fastness to light. Dyes of the formula (Ia): w

in which X is hydrogen or chloro; Y is hydrogen, chloro or nitro; Z is hydrogen or nitro;

'K is the radical of a coupling component of the acetoacetarylide, pyridone, pyrimidone and particularly of the 2-naphthol-3-carboxylic arylamide series; and

R is unsubstituted or substituted phenyl or naphthyl are of particular industrial significance.

Coupling components of the pyridone and pyrimidone series do not contain any substituents on the nitrogen atom. More particular dyes of the invention are those of the formula (lb):

inwhich Q, HO ,N

I I N QH Ho N OH 3 WOH OH coma-m Ar is phenyl or phenyl substituted by chloro, methoxy, ethoxy, methyl,

Ar is phenyl or phenyl substituted by chloro methyl, Ar" is phenyl, phenyl substituted by chloro, methoxy,

4 methyl, phenylaminocarbonyl, chlorophenylaminocarbon yl, dichlorophenylaminocarbonyl, phthaloylam inophenylaminocarbonyl, an-

thraquinonylamino-carbonyl, benzoylaminophenylaminocarbonyl, sulfonylphenylamone-carbonyl, N-(phehylsulfamoylor N-chlorophenylsulfamoyl)-' phenylamimocarbonyl, phthaloylaminobenzoylamino, chlorobenzoylamino, anthraquinonylcarbonylamino or ethylphenylaminocarbonyl or naphthyl or phenylami-' nooxalylamino, T is methyl or carbamoyl, T is cyano or carbamoyl, T is NH or OH with the proviso that al least one is NH2, R is phenyl, phenyl substituted by chloro, b'romo, methyl, methoxy, cyano, nitro, phenyl, sulfamoyl, N- phenylsulfamoyl, phenylsulfonyl, acetylamino, benzoylamino or dichlorobenzoylamino, naphthyl or anthraquinonyl, X is hydrogen or chloro Y is hydrogen, chloro or nitro and Z is hydrogen or nitro.

The following Examples illustrate the invention. Unless otherwise stated references to parts and percentages in the Examples are by weight.

EXAMPLE 1 14.1 parts of 2(2'-phenyloxidazoly1-l,3-4)-4- nitroaniline is introduced at 10 to 15C into 100 parts of sulfuric acid, cooled to 0 to 5C and diazotized by adding 15 parts of nitrosylsulfuric acid (12.7% of N 0 The whole is stirred for another three hours at 5C. The mixture is then poured onto a mixture of 400 parts of ice and 600 parts of water. 13.2 parts of finely powdered 2-naphthol-3-carboxylic N-phenylamide is added and dilute caustic soda solution is dripped in until a pH of from 6 to 7 has been set up. The whole is stirred for another six hours, suction filtered and washed thoroughly with water. The filter cake is introduced into 200 parts of dimethylformamide, stirred for three hours at C, suction filtered, washed thoroughly with methanol and dried. 24 parts of a red powder is obtained having the formula:

Dyes corresponding to the coupling components given in the following Table and having the hues indicated are obtained analogously to Example 1.

Example Coupling c omponent Hue 2 red oer CONH-Q-Cl ---Continued Example Coupling component Hue OH CONH- OCH OH CONH ;-CH

OH 5 orange 6 CH -COCH -C0NH ellow 7 CH COCH -CONH H o yllow 8 CH COCH -CONH yellow 9 m yellow OH 10 w yellow H 0H 11 W 11 N N ye ow 12 Ho H2 FN yellow NH -Continued Hue Example Coupling component yellow yellow yellow CONH yellow yellow 17 CH3-COCH2CONHQ OCH yellow yellow yellow Continued ExlaImple Coupling Component Hue o v r i 21 yellow OH Cl 22 (n Bordeaux C ONH OCH OH 25 a): red

COOCH OH CH3 26 CO-NH red EXAMPLE 27 (,5 coupling component. After coupling is over the whole is acidified to pH 1 with dilute sulfuricacid, suction fil- The procedure described in Example 1 is followed tered, washed thoroughly with water and dried. 21 but 9.4 parts of B-hydroxynaphthoic acid is used as the parts of the acid:

N one hour at 90C, one hour at 110C and 2 hours at 120C. The whole is suction filtered hot, washed with O dichlorobenzene and dried. 40 parts of a red powder of I 5 the formula: R N N 02 N O N N COOH N 0H is obtained. 481 parts of this acid 18 heated in 2200 m parts of dry dichlorobenzene, 2 parts of dimethylform- CO-NH--CONH- amide and 350 parts of thionyl chloride for 1 hour at C, for two hours at C and for 1 hour at C, is Obtained in this way then cooled, suction filtered when cold, washed with dry benzene and dried. 295 parts of the acid chloride is EXAMPLES 8 to 67 thus 0btalrl6 t The procedure described in Example 27 is followed 25 Parts ofthls acld chlol'lde 15 added to 20 but the amines specified in the following Table are used parts of y dlchlol'obenlene, 22 Parts Of p-ammoinstead of p-aminobenzoanilide. The corresponding benzoanilide is added and the whole is stirred for dyes are obtained and have the hues indicated:

Example Amine Hue Cl 29 NH Q-CO-NHGCl red 50 NH2--CONHQ red 52 NHQQCO-NH-Q 0 red 3 Bordeaux ,4

Continued Example Amine Hue CH3 5 NH2CO-NH-QH;\2 Bordeaux 0 35 NHE-Q-CONH-Q-CONHQ red 0 7 36 NHQG-CONH red o 57 NHZ-Q C1 rd CO-NHQ 58 NH2 red 90 CONH N K) co 0 39 HEN co- :1 fed 0 4O NH Q-Cl red -co-NH-NH-co- 41 NH2-QC0-NH-C\ -NH-CO- red NH2 OCH} red -Continued Example Amine Hue 52 NH2--NH-CO- red ,c0 55 NH @NH-CO-Q-N 1) red 01 5 NH2--NH-CO-C1 red 01 c1 55 NH2C-NH-COC1 red 56 NH2-NHCO Cl red (L053 c1 57 NHEGNH-CO co red 58 NH2 Cl maroon NH co CO\ OCH} 59 NHECE-CH5 Bordeaux NH-CO CO 01 UCO OCH} 6O NHZ-GNH-CO CO' Bordeaux 61 red NH-CO N wi -Q D Continued Example Amine Hue NHEQ-NH-COQ Cl z 66 NHQ-G-NH-CO I) EXAMPLE 68 30.5 parts of 2-(2-phenyloxdiazolyl-l ',3'-4')-4,6- dichloroaniline is introduced at from to C into 200 parts of 85% sulfuric acid, cooled to 0 to 5C and diazotized at 5 to 10C by adding parts of nitrosylsulfuric acid (12.7% of N 0 and stirring for 4 hours. The diazo solution is poured while stirring into a mixture of 400 parts of ice and 700 parts of water, 26 parts of Z-naphthol-3-carboxylic-N-phenylamide is added and a pH of from 6 to 7 is set up by dripping in dilute caustic soda solution. The whole is stirred for 8 hours, suction filtered, washed thoroughly, the moist filter cake is suspended in 5000 parts of methyl glycol and stirred for two hours at 1 10C. After suction filtration, washing with methanol and drying parts of a red powder of the formula:

maroon red red

Bordeaux red Bordeaux OH o is obtained.

As described in Example 68 dyes having the hue indicated in the following Table are obtained with the diazo Diazo component for EXAMPLES 69 TO 81 Ex. No. Coupling component I Hue CO-NHQCO-NH red OH 70 orange CN 71 I yellow H N OH 5 CN 7 yellow Disp.

H I I O z 75 I yellow 7 m yellow CH5 75 \5 yellow Disp.

OH I! ll 76 -Continued Ex. No. Coupling component Hue OH 77 w Cl red co-NH-NH-coc1 OH 78 oo CO-NHQ red NH-CO 0 C1 CO OH OCH3 79 yellow Disp.

1 CH CH 5 5 CN 80 I n n HO O CH -CH -CH --CH -OCH3 OH yellow Diazo components for Examples 82 to 85 C I I H N OH orange 82 oo OH 85 @g O-NH red Disp CO-NHNH-CO red Continued Ex.No Coupling component Hue OH 5 we co T red H l v 86 Cl red CO-NH-NH-CO\@CO)\I C1 O-NHQ-CO-NH OH c1 89 yellow CH 5 90 N yellow Dlsp.

5 CN 91 yellow I HO N OH 3 92 I CN yellow Djsp.

CH I

95 i n n O- 4 I CH 3 94 --CH C0CH CONH 0 yellow Continued Ex. Diazo component Coupling component Hue Ex. Diazo component Coupling component Hue H 0 red I l CO-NHQCl c1 HN co-NHcl OH 97 O @i 01 01 red HEN l co-NH-coNH-coc1 OH red 98 II I! CONHNH-CO\@[;3O

4 OCH OH C1 5 99 CO-NHQ-CO-NH red OH 100 m I red I I CO-NH z N-N Ex. Diazo component Coupling component Hue N0 101 C1 OH d o4mc1 H OH 102 w: red

H OCH o 3 105 u @H Cl Fed O-NHQCb-NH Continued Ex. Diazo component Coupling component Hue O CONH@ a 01 105 01 red CO-NHQCO-NHQ c1 dull NO Cl OH 1 1 109 0 w 00 red I l Q EJO 2 OH Cl 110 H @TJC n O-NH OCH 1 111 OH red o no I l CO-NH-G E NN -Continued Ex. Diazo component Coupling component Hue 2 OH (:1 121 we red 0 ONH-Q-CONH NH com1 c1 0 NH2 N0 125 N OH red J-QNO com-Q NH on CONHQ-CONHQ ellow 125 u n I y 2 Cl red 126 01 N\N CH com-@com ONHCONH Fed m OCH (:1 c1

128 n H @OH red com-Q 129 Bordeaux I CONH OCH Continued Ex. Diazo component Coupling component Hue H /N NH- red CONHQ O NH H 3 @[Z Bordeaux ONHOCH3 NO OH CONH O 2 OH 33 N N red I com-@m o NH2 3 1 1- NO N -N 5 2 I A yellow No OH 135 (E i): red

CONH NH2 OH 136 H n @1 CH5 red CONH 157 OH 00H Bordeaux CONH ocH

OH OCH orange CONH Continued Ex Diazo component Coupling component Hu e II I! EXAMPLES OF APPLICATION 1: in surface coating parts of the dye obtained according to Example 1 and 95 parts of baking finish mixture (for example 70% of coconut alkyd resin, 60% in xylene and of melamine resin, about 55% in butanol/xylene) are ground in an attrition mill. The product is applied and baked for thirty minutes at 120C. Bright red full shade surface coatings are obtained having very good light fastness and fastness to overspraying. Bright white shades are obtained by adding titanium dioxide.

When pigments (other than disperse dyes marked Disp.) in the other Examples are used, similar surface coatings are obtained in the hues given.

2: in plastics Bright polystyrene coloration having excellent fastness to light may be obtained by incorporating 0.5 part of the dye obtained according to Example 1 into 100 parts of polystyrene at 190 to 200C in an extruder.

Colorations having good hiding power are obtained analogously when 1 part of titanium dioxide is incorporated as well.

Analogous results are obtained by using pigment dyes from the other Examples except those marked Disp..

3: in printing ink 8 parts of the pigment obtained according to Example 1, 30 to parts of resin (for example rosin modified with phenol-formaldehyde) and to parts of toluene are intimately mixed in a dispersing machine. A red toluene intaglio printing ink is thus obtained having OH CH CONH N-N OH 0 CONH NH OH @CONHQCl OCH C ONH red red

red

red

C1 Bordeaux OCH outstanding light fastness, weather fastness and brightness. v

Analogous results are obtained when the pigments 45 from the other Examples, except those marked Disp.

are used.

We claim:

1. An azo dye of the formula Y N =N-K l OYN in which K is i Ol-1 4. a S 3 2 T OH (Ir r n A N N N/ on H0 N H 

1. AN AZO DYE OF THE FORMULA
 2. A dye of the formula according to claim 1, wherein K is
 3. A dye of the formula according to claim 1, wherein K is
 4. A dye of the formula according to claim 1, wherein K is
 5. The dye according to claim 1 of the formula 